SUPPORTING INFORMATION

Transcription

1 SUPPORTING INFORMATION USEFULNESS OF A DUAL MACRO AND MICRO ENERGY DISPERSIVE X-RAY FLUORESCENCE SPECTROMETER TO DEVELOP QUANTITATIVE METHODOLOGIES FOR HISTORIC MORTAR AND RELATED MATERIALS CHARACTERIZATION Cristina García-Florentino*, Maite Maguregui, Miriam Romera-Fernández δ, Ignasi Queralt γ, Eva Marguí λ and Juan Manuel Madariaga *Corresponding author: cristina.garciaf@ehu.eus Department of Analytical Chemistry, Faculty of Science and Technology, University of Basque Country UPV/EHU, P.O. Box 644, Bilbao, Basque Country, Spain, * cristina.garciaf@ehu.eus Department of Analytical Chemistry, Faculty of Pharmacy, University of the Basque Country UPV/EHU, P.O. Box 450, 01080, Vitoria-Gasteiz, Basque Country, Spain δ MINERSA Group, C/Jaén nº1, 3º, Bilbao, Basque Country, Spain γinstitute of Environmental Assessment and Water Research. IDAEA-CSIC. Jordi Girona 18-26, Barcelona, Spain. λ Department of Chemistry, University of Girona, Faculty of Sciences, C/ M.Aurèlia Campmany, 69, Girona, Spain. Table of contents Supplementary Figures: Figure from S-1 to S-4 Supplementary Tables: Tables from S-1 to S-9

2 Supplementary Figures Figure S-1. A zoom (1-4 kev) of the ED-XRF spectra obtained for two different of the same mortar sample (MER) prepared with two different binders (elvacite and wax) and measured at two different voltages each one (for the best detection of both light and heavy elements). Figure S-2. Calibration curves for some of the calibrated elements based on the use of synthetic standards.

3 Figure S-3. Calibration curves for some of the calibrated elements based on the use of CRMs.

4 Figure S-4. Flow chart summarizing the different steps to develop an accurate quantitative µ-ed-xrf methodology.

5 Supplementary Tables Table S-1. Mean net intensity (counts) and relative standard deviation (RSD%) values for 50 points randomly distributed and measured at 1mm lateral resolution and for 150 points randomly distributed and measured at 25 µm lateral resolution for the synthetic standard STD-4. Concentration (mg/kg) Mean net counts (1 mm) RSD% (1 mm) Mean net counts (25 µm) RSD% (25 µm) Na 5895 <LOD <LOD Mg Al Si P x N.C x N.C x S Cl K Ca Ti Mn Fe Zn Rb Sr x N.C x N.C x Ba Pb N.C Non-calibrated Table S-2. ED-XRF quantitative estimation for BCR-032 and 634a Portland Cement Certified Reference Materials using the FP-method implemented in the ED-XRF spectrometer (measured done at 1mm spatial resolution). Results expressed in mg/kg. BCR-032 (ED-XRF BCR-032 certified 634a PC (ED-XRF 634a PC certified quantification) concentration quantification) concentration Na <LOD 6380* <LOD 620 ± 20 Mg <LOD 2410 ± ± ± 50 Al 2600 ± ± ± ± 100 Si 5800 ± ± ± ± 300 S 5700 ± ± ± ± 300 Cl <LOD Non-certified <LOD Non-certified K 1730 ± * 3080 ± ± 30 Ca ± ± ± ± 2000 Ti 350 ± ± ± ± 20 Mn <LOD 19 ± ± ± 8 Fe 3700 ± ± ± ± 200 Zn 490 ± ± ± ± 20 Rb <LOD Non-Certified <LOD Non-Certified Ba <LOD Non-Certified <LOD Non-Certified Pb <LOD 5.4* <LOD Non-Certified <LOD Under Limit Of Detection, *estimated values in the certification

6 Table S-3. Calibration ranges (expressed in mg/kg), XRF-lines used for the quantification, coefficients of determination obtained for each calibration curve and Limits of Detection (expressed in mg/kg) for the calibrated elements in the synthetic standards. Calibration range R 2 LOD Calibration range R 2 LOD Na (K α ) <LOD x <LOD Ti (K α ) Mg (K α ) Mn (K α ) Al (K α ) Fe (K α ) Si (K α ) Sr (K α ) Non-calibrated x x P (K α ) Non-calibrated x x Zn (K α ) S (K α ) Rb (K α ) Cl (K α ) Ba (L α ) K( K α ) Pb (L α ) Ca (K α ) x x x x LOD calculated according to LOD = Table S-4. Concentrations calculated (in mg/kg) for BCR-032 and NIST-634a Portland Cement Certified Reference Materials and relative errors (absolute values) using the calibration methodology based on the use of synthetic standards. BCR-032 BCR-032 NIST-634a PC NIST-634a PC calculated values Certified values calculated values Certified values Na <LOD 6380 b x <LOD 620 ± 20 x Mg <LOD 2410 ± 60 x <LOQ 6060 ± 50 x Al 2500 ± 300 a 5800 ± ± ± Si ± 400 a 9700 ± ± ± P Non-calibrated ± 700 x Non- calibrated 770 ± 10 x S 3700 ± ± ± ± Cl <LOD Non-certified x <LOD Non-certified x K 1520 ± 60 a 747 b ± ± 30 3 Ca ± ± ± 6000 c ± Ti 90 ± 10 a 171 ± ± ± Mn <LOD 19 ± 1 x 55 ± ± 8 65 Fe <LOQ 1600 ± 70 x ± ± Zn 199 ± ± ± ± Rb <LOD Non-certified x <LOD Non-certified x Sr N.C Non-certified x Non-calibrated 620 ± 40 x Ba <LOD Non-certified x <LOD Non-certified x Pb <LOD 5.4 b x <LOD Non-certified x a These values were estimated by extrapolation under the standard with the lowest concentration value in the calibration b These values were expressed as indicative in the certification c This value was estimated by extrapolation over the standard with the highest concentration value in the calibration

7 Table S-5. Calibration ranges (expressed in mg/kg), XRF-lines used for the quantification, coefficients of determination and Limits of Detection for the calibrated elements (expressed in mg/kg) for the quantification strategy based on the use of CRMs as standards. Calibration R 2 LOD Calibration R 2 LOD range range Na (K α ) x <LOD Ti (K α ) Mg (K α ) Mn (K α ) Al (K α ) Fe (K α ) Si (K α ) Sr (K α ) P (K α ) Zn (K α ) Non-calibrated x x S (K α ) Rb (K α ) Non-calibrated x x Cl (K α ) Non-calibrated x x Ba (L α ) Non-calibrated x x K( K α ) Pb (L α ) Non-calibrated x x Ca (K α ) LOD calculated according to LOD = 588 x x x x Table S-6. Mean net intensity (counts) and relative standard deviation (%RSD) values for 50 points randomly distributed at 1mm lateral resolution and for 150 points randomly distributed at 25 µm lateral resolution for the CRM 601-B1 pellet. Mean net counts (1mm) %RSD (1mm) Mean net counts (25 µm) %RSD (25 µm) Na <LOD x Mg <LOD x Al Si P S Cl Non-Calibrated x Non-Calibrated x K Ca Ti Mn Fe Zn Non-Calibrated x Non-Calibrated x Rb Non-Calibrated x Non-Calibrated x Sr Ba Non-Calibrated x Non-Calibrated x Pb Non-Calibrated x Non-Calibrated x

8 Table S-7. Concentrations calculated (in mg/kg) for NIST-634a Portland Cement Certified Reference Material and relative errors (absolute values) using both WD-XRF quantification methods. NIST-634a PC NIST-634a PC Fused beads NIST-634a PC Certified values Fused beads Na 1000 ± ± ± Mg 6200 ± ± ± Al ± ± ± Si ± ± ± P 820 ± ± ± S ± ± ± Cl Non-calibrated Non-calibrated Non-certified x x K 3100 ± ± ± Ca ± ± ± Ti 1460 ± ± ± Mn 130 ± ± ± Fe ± ± ± Zn Non-calibrated Non-calibrated 180 ± 20 x x Rb Non-calibrated Non-calibrated Non-certified x x Sr 640 ± ± ± Ba Non-calibrated Non-calibrated Non-certified x x Pb Non-calibrated Non-calibrated Non-certified x x Table S-8. Concentrations calculated (in mg/kg) for BCR-032 Certified Reference Material and relative errors (absolute values) using both WD-XRF quantification methods. BCR-032 BCR-032 Fused beads BCR-032 Certified values Fused beads Na 5400 ± ± a Mg 3110 ± ± ± Al 3800 ± ± ± Si ± ± ± P ± ± ± S 4920 ± ± ± Cl Non-calibrated Non-calibrated Non-certified x x K ± a 9 21 Ca ± ± Ti ± ± Mn <LOQ <LOQ 19 ± 1 x x Fe ± ± Zn Non-calibrated Non-calibrated 253 ± 6 x x Rb Non-calibrated Non-calibrated Non-certified x x Sr ± 20 Non-certified x x Ba Non-calibrated Non-calibrated Non-certified x x Pb Non-calibrated Non-calibrated 5.4 a x x a These values were expressed as indicative in the certification

9 Table S-9. Elemental characterization of a concrete sample (CS1) using the developed ED-XRF and WD-XRF methods based on the use of CRM standards and by WD-XRF method based on the use of fused beads. Concentration units in mg/kg. CS1 ED-XRF CRM WD-XRF CRM WD-XRF fused beads Na <LOD 1480 ± ± 500 Mg ± ± ± 1000 Al ± ± ± 5000 Si ± ± ± P <LOD 530 ± ± 30 S 4490 ± ± ± 1000 Cl Non-calibrated Non-calibrated Non-calibrated K 3570 ± ± ± 500 Ca ± ± ± Ti 2460 ± ± ± 80 Mn 1700 ± ± ± 100 Fe ± ± ± 7000 Zn Non-calibrated Non-calibrated Non-calibrated Rb Non-calibrated Non-calibrated Non-calibrated Sr 1930 ± ± ± 50 Ba Non-calibrated Non-calibrated Non-calibrated Pb Non-calibrated Non-calibrated Non-calibrated